Aromatic Rearrangements in Which the Migrating Group Migrates to the Aromatic Nucleus

Snape, Timothy J.

doi:10.1002/9781118754887.ch18

Cited by 2 publications

(2 citation statements)

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“…In our previous work, we established that the related aminative rearrangement of sulfonyl O -hydroxylamines proceeded via an intermolecular mechanism, shown by extensive scrambling in crossover experiments. 18,23 In contrast, analogous experiments in the present system— i.e. subjecting carboxyl substrates 1b (delivering NH 2 ) and 3i (delivering NHMe) afforded no product crossover, which suggested that the reaction might proceed via an intramolecular mechanism (Scheme 3A).…”

Section: Resultsmentioning

confidence: 54%

Ortho-Selective amination of arene carboxylic acids via rearrangement of acyl O-hydroxylamines

Gillespie,

Lam,

Phipps

2023

Chem. Sci.

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Section: Resultsmentioning

confidence: 54%

Ortho-Selective amination of arene carboxylic acids via rearrangement of acyl O-hydroxylamines

Gillespie,

Lam,

Phipps

2023

Chem. Sci.

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“…Despite many reports of catalytic onium ylide rearrangements of aliphatic systems, , only a few examples of analogous aromatic rearrangements are known which are limited to sulfonium (X = SR) and ammonium (X = NR 2 ) ylides . The challenge of developing this class of rearrangements is partially due to the energetic penalty associated with disruption of aromaticity in the sigmatropic [2,3]-rearrangement (Scheme A) . A pioneering study on catalytic thia-Sommelet-Hauser rearrangement was reported by Wang and co-workers in 2008 .…”

Section: Introductionmentioning

confidence: 99%

Catalyst-Controlled Regiodivergence in Rearrangements of Indole-Based Onium Ylides

et al. 2021

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We have developed catalyst-controlled regiodivergent rearrangements of onium-ylides derived from indole substrates. Oxonium ylides formed in situ from substituted indoles selectively undergo [2,3]-and [1,2]-rearrangements in the presence of a rhodium and copper catalyst, respectively. The combined experimental and density functional theory (DFT) computational studies indicate divergent mechanistic pathways involving a metal-free ylide in the rhodium catalyzed reaction favoring [2,3]-rearrangement, and a metal-coordinated ion-pair in the copper catalyzed [1,2]-rearrangement that recombines in the solvent-cage. The application of our methodology was demonstrated in the first total synthesis of the indole alkaloid (±)-sorazolon B, which enabled the stereochemical reassignment of the natural product. Further functional group transformations of the rearrangement products to generate valuable synthetic intermediates were also demonstrated.

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Aromatic Rearrangements in Which the Migrating Group Migrates to the Aromatic Nucleus

Cited by 2 publications

References 100 publications

Ortho-Selective amination of arene carboxylic acids via rearrangement of acyl O-hydroxylamines

Ortho-Selective amination of arene carboxylic acids via rearrangement of acyl O-hydroxylamines

Catalyst-Controlled Regiodivergence in Rearrangements of Indole-Based Onium Ylides

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